CN109370287A - A kind of hydrogel being sustained silicone oil and its application in marine antifouling coating - Google Patents
A kind of hydrogel being sustained silicone oil and its application in marine antifouling coating Download PDFInfo
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- CN109370287A CN109370287A CN201811215424.4A CN201811215424A CN109370287A CN 109370287 A CN109370287 A CN 109370287A CN 201811215424 A CN201811215424 A CN 201811215424A CN 109370287 A CN109370287 A CN 109370287A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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Abstract
The present invention relates to the self-repair technology fields of nonpolluting coating, disclose a kind of hydrogel for being sustained silicone oil and its application in marine antifouling coating.The monomer for preparing the hydrogel rubber shell is acrylamide, N hydroxymethyl acrylamide, n-isopropyl acrylamide and alkyl propionates or acrylate.The preparation method simple possible of the hydrogel of sustained release silicone oil of the invention, it is highly-safe, it can be realized industrialized production, there are large development potentiality.The hydrogel of the sustained release silicone oil is applied in marine antifouling coating, the compatibility of methyl-silicone oil Yu the other components of coating can be improved, control the rate of release of methyl-silicone oil in coating, extend the validity period of methyl-silicone oil effect, the maintenance for being conducive to the coating microstructure with anti-pollution function makes up insufficient in existing methyl-silicone oil application technology.
Description
Technical field
The present invention relates to the self-repair technology field of nonpolluting coating more particularly to it is a kind of be sustained silicone oil hydrogel and its
Application in marine antifouling coating.
Background technique
Silicone oil is a kind of polysiloxane of chain structure, is widely used, and is it using it for marine antifouling coating
One.It is used for marine antifouling coating as additive, silicone oil can to change the surface state of paint coatings, and it is free to reduce coating surface
Can, make marine organisms be not easy to adhere to.But the low polarity of silicone oil, it is very poor with the other composition compatibilities of coating, easily there is coating table
Face transport phenomena, to influence the service performance and validity of antifouling paint.
The patent of Chinese patent application Publication No. CN106928797A discloses a kind of reversible selfreparing antimicrobial acrylic
Coating, preparation and self-repair method.This method is by methyl methacrylate, butyl acrylate, sulfonyl glycine betaine metering system
Acid esters, acetoacetate methacrylic acid glycol ester are added in alcoholic solvent, cause free radical polymerization by azodiisobutyronitrile, obtain
To linear propylene's acid resin.Linear propylene's acid resin and amino-containing hyperbranched polyorganosiloxane are dissolved in alcoholic solvent, are coated on
Substrate surface obtains a kind of reversible selfreparing antimicrobial acrylic coating after dry.Although the coating can be realized selfreparing, but
Selfreparing needs just to be able to achieve within 8~24 hours in 60~120 DEG C of at a temperature of processing.The coating selfreparing is needed by extraneous item
Part cannot achieve selfreparing at normal temperature.
Summary of the invention
It is applied in order to solve the above-mentioned technical problems, the present invention provides a kind of hydrogel for being sustained silicone oil and its in marine anti-pollution
Application in material.The hydrogel coats the microcapsules that methyl-silicone oil is formed, and can be sustained methyl-silicone oil, to repair the anti-of damage
Dirty coating surface ensure that the long effect of anti-fouling effect.The hydrogel preparation process of the sustained release silicone oil is simple, is suitble to extensive raw
It produces.
The specific technical proposal of the invention is: a kind of hydrogel for being sustained silicone oil, the hydrogel of the sustained release silicone oil include
Hydrogel rubber shell and the methyl-silicone oil being supported in hydrogel rubber shell, the hydrogel rubber shell are by monomer A, monomer B, monomer C
With polymer made of monomer D copolymerization, structural formula are as follows:
Wherein, R1For H or CH3；R2For CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、CH3CH2CH2CH2One or more of；m
For the positive integer not less than 10；N is the positive integer not less than 10；P is 0 or positive integer；Q is the positive integer not less than 1, and is controlled
Corresponding monomer is no more than 10% relative to the score of the amount of other monomer total materials, and m, n, p, q value control polymer number
Average molecular weight is not less than 4000.
The hydrogel of sustained release silicone oil of the invention be specific to silicone-contained acrylic resin solution latex base marine antifouling coating and
Specially design.Hydrogel rubber shell of the invention is acrylamide, N hydroxymethyl acrylamide, n-isopropyl acrylamide and third
The polymer that acid alkyl ester or acrylate are formed.Marine antifouling coating mostly uses silicone-contained acrylic resin solution latex solution to be made,
The hydrogel of sustained release silicone oil prepared by the present invention is used in marine antifouling coating, methyl-silicone oil can be enhanced and marine anti-pollution applies
The compatibility of material.When marine antifouling coating surface abrasion, the hydrogel for being sustained silicone oil can release methyl-silicone oil, release
Methyl-silicone oil by breakage by silicon oxygen bond reconnect together, realize nonpolluting coating selfreparing purpose.
The ductility and swelling ratio of the hydrogel formed when individually with acrylamide are high, but the intensity of hydrogel is lower, hold
It is easy to wear.Be added into be easy to cause in marine antifouling coating its rate of wear than marine antifouling coating the rate of wear more
Fastly, cause methyl-silicone oil to release in advance, shorten the selfreparing period of marine antifouling coating.When with monomer N- methylol third
When acrylamide and n-isopropyl acrylamide polymerize together, acrylamide, N hydroxymethyl acrylamide and N- isopropyl acrylamide
Amide groups and hydroxyl on amine are capable of forming intramolecular or/and intermolecular hydrogen bonding, increase the rigidity of hydrogel.In addition, and monomer
Alkyl propionates or acrylate polymerize together, increase high molecular branch quantity, and then increase the rigidity of material.This hair
Monomer N hydroxymethyl acrylamide is no more than relative to the score of the amount of other monomer total materials in the hydrogel rubber shell of bright preparation
10%, increase with the amount of N hydroxymethyl acrylamide, the hydrophily enhancing of high molecular material, it will lead to the antifouling energy of material
Power weakens, and the antifouling capacity of marine antifouling coating will be reduced by adding it in marine antifouling coating, this is to mesh of the invention
It is very unfavorable.The intensity and hydrophobicity of compound material, inventor is after largely testing by N hydroxymethyl acrylamide
Amount is limited to 10% of the amount score no more than other monomer total materials.The molecular weight of hydrogel rubber shell of the invention is not less than
4000, when molecular weight is too low, the intensity difference of material is easy to wear, will shorten the selfreparing period of marine antifouling coating.Of the invention
Principal monomer is acrylamide and alkyl propionates or acrylate, N hydroxymethyl acrylamide, N- isopropyl in conjunction with a part
The sustained release Silica hydrogel rubber shell of base acrylamide, formation is suitable with the intensity of marine anti-pollution coating, is ground in marine anti-pollution coating
Methyl-silicone oil can timely be released when damage to be repaired, while the hydrogel rubber shell has suitable gap, normal non-mill
Methyl-silicone oil will not be discharged under the conditions of damage, and there is preferable hydrophobic performance.
Preferably, preparation method includes the following steps for a kind of hydrogel for being sustained silicone oil:
(1) at room temperature, surfactant, monomer A, monomer C, monomer D, methyl-silicone oil and initiator are mixed, obtains premixed material；
(2) monomer B and surfactant are added to the water, the mass volume ratio of monomer B and water is 4~5g/30mL, while stirring
45~55 DEG C are warming up to, mixed solution is obtained；Then the premixed material in step (1) is even with the rate of addition of 0.5~0.75mL/min
Speed is added drop-wise in mixed solution, is stirred when being added dropwise with the rate of 900~3000r/min, is reacted 9~11h, must be sustained silicone oil
Hydrogel.
The present invention first at room temperature by the surfactant of a part, monomer A, monomer C, monomer D, methyl-silicone oil and draw
Hair agent is mixed, and uniform premixed material is made.Monomer B and remaining surfactant is soluble in water, it stirs, be warming up to 45
After~55 DEG C, the premixed material in step (1) is at the uniform velocity added drop-wise in mixed solution with the rate of addition of 0.5~0.75mL/min,
Liquid is stirred with the rate of 900~3000r/min when being added dropwise, and maintains 45~55 DEG C of 9~11h of reaction and forms sustained release silicon
The hydrogel of oil.The present invention needs strict control premixed material to the speed of the mixed solution and dripping of monomer and surfactant,
Rate of addition is too fast, is easy to cause the hydrogel coating of sustained release silicone oil incomplete, and the partial size of the hydrogel of the sustained release silicone oil of formation is not
Uniformly；Rate of addition is excessively slow, and the aqueous monomers of polyamide will tend to bulk polymerization, without being copolymerized with other monomers, by nothing
Method obtains the high molecular material with structure of the invention, and can not form complete water since the bulk polymerization of polyamide will lead to
The hydrogel local strength of gel or formation is too low.The present inventor obtains by a large amount of experiment and prepares sustained release silicon of the invention
The equalization point of the hydrogel of oil, i.e., by controlling dropping temperature and rate of addition in 45~55 DEG C and 0.5~0.75mL/min
To control reaction speed of the invention.Meanwhile the reaction time of the invention also needs strict control, the reaction time is too long, formation
The crosslinking degree of hydrogel rubber shell is higher, and methyl-silicone oil is less susceptible to be released；Reaction time is too short, will lead to be formed
The hydrogel coating of sustained release silicone oil is not complete or rubber shell thickness is excessively thin.Preparation process of the invention is simple, strong operability, is suitble to big rule
Mould production.
Preferably, the monomer A, monomer B, the total amount of monomer C and monomer D and surfactant total amount, methyl silicon
The mass ratio of oil and initiator is 240~260:1:100:6~7.When surfactant, monomer, methyl-silicone oil and initiator
When total mass ratio is 1:240~260:100:6~7, the hydrogel coating of the sustained release silicone oil of preparation is complete, the rubber shell thickness of rubber shell
It is most uniform with average grain diameter.When monomer is very few, the hydrogel coating that will lead to the sustained release silicone oil to be formed is not complete；When monomer is very few
When, the hydrogel rubber shell that will lead to the sustained release silicone oil to be formed is blocked up, and the methyl-silicone oil of cladding is not easy to release.
Preferably, the monomer A be methyl propionate, methyl methacrylate, ethyl propionate, ethyl methacrylate,
Propyl propionate, propyl methacrylate, isopropyl propionate, isopropyl methacrylate, butyl propionate, in butyl methacrylate
At least one, monomer B be acrylamide, monomer C be n-isopropyl acrylamide, monomer D be N hydroxymethyl acrylamide.
Preferably, the surfactant is in lauryl sodium sulfate, OP-10, TX-10, paregal O or Tween 80
At least one.
Preferably, the initiator is that potassium peroxydisulfate, ammonium persulfate, V-50 initiator, azo isobutyronitrile, azo two are different
At least one of heptonitrile, dioctanoyl peroxide, benzoyl peroxide.
A kind of application of the hydrogel in marine antifouling coating being sustained silicone oil, the marine antifouling coating includes siliceous third
Olefin(e) acid resin emulsion solution and sustained release silicone oil hydrogel.
The hydrogel of sustained release silicone oil of the invention can be realized marine anti-pollution in conjunction with silicone-contained acrylic resin solution latex solution
The hydrogel of the long-term selfreparing of coating, the sustained release silicone oil that the present invention designs is suitable with the wearability of marine antifouling coating, with
The abrasion of marine antifouling coating, for hydrogel rubber shell also by the abrasion of equal extent, the hydrogel for being sustained silicone oil will release first
Base silicone oil, methyl-silicone oil are connected the fray of marine antifouling coating by silicon oxygen bond, realize the selfreparing of marine antifouling coating.
Preferably, the marine antifouling coating the preparation method comprises the following steps: by silicone-contained acrylic resin solution latex solution 25~70
Part, 1~10 part of plasticizer, 1~20 part of filler material, 1~10 part of hydrogel for being sustained silicone oil and 5~40 parts of anti-fouling agent are shaking together
2~4h of vibration in device is swung, is filtered with the filter of 70~90 mesh, obtains marine antifouling coating.
Preferably, the marine antifouling coating includes the raw material composition of following parts by weight: silicone-contained acrylic resin solution cream
54~70 parts of sol solution, 1~4 part of plasticizer, 1~5 part of filler material, 6~10 parts of hydrogel for being sustained silicone oil and anti-fouling agent 31~
35 parts.
Each reasonable raw material proportioning of marine antifouling coating of the invention has good intensity and anti-pollution, reviews one's lessons by oneself reactivation
Power is strong, and the selfreparing period is long, and preparation process is simple, is suitble to large-scale production.
Preferably, the concentration of the silicone-contained acrylic resin solution latex solution is 30~60wt%；Plasticizer be vaseline,
At least one of chlorinated paraffin, dibutyl phthalate or dioctyl phthalate；Filler material is iron oxide red, talcum
At least one of powder, titanium dioxide, lithopone, fumed silica solid particle or zinc oxide；Anti-fouling agent is cuprous oxide
And/or the mixing of tetramethylthiuram disulfide and/or pyrithione and/or triphenylboron pyridine and/or Seanine-211
Object.
It is compared with the prior art, the beneficial effects of the present invention are: the hydrogel of sustained release silicone oil of the invention can under abrasion
Methyl-silicone oil is slowly discharged, the rate of release of coating methyl-silicone oil is controlled, improves the phase of methyl-silicone oil with the other components of coating
Capacitive, extending methyl-silicone oil effect validity period to repair the nonpolluting coating surface of damage ensure that the long effect of anti-fouling effect
Property.
Specific embodiment
The present invention will be further described with reference to the examples below.Related device, connection structure in the present invention
And method, if being device well known in the art, connection structure and method without refering in particular to.
Embodiment 1
A kind of preparation for the hydrogel being sustained silicone oil, the specific steps of preparation are as follows:
(1) at room temperature, by 20g methyl methacrylate, 5g N hydroxymethyl acrylamide, 20g methyl-silicone oil, 0.1g 12
Sodium alkyl sulfate is added in emulsion dispersion machine, with ultrasonic dispersers ultrasonic disperse 1h, then under the stirring at low speed of 280r/min
1.2g azodiisobutyronitrile is added, is mixed to obtain premixed material.
(2) it in four mouthfuls of reaction flasks for being equipped with blender, addition funnel, reflux condensate device, thermometer, is added
150mL water, 25g acrylamide, 0.1g lauryl sodium sulfate, stir and evenly mix, and are warming up to 50 DEG C, then by premixed material with
The rate of addition of 0.65mL/min is at the uniform velocity added drop-wise in acrylamide and the mixed solution of lauryl sodium sulfate, while be added dropwise while with
The rate of 900r/min is stirred solution, maintains 50 DEG C and continues to be stirred to react 10h, must be sustained the hydrogel of silicone oil.
A kind of application of the hydrogel in marine antifouling coating being sustained silicone oil, marine antifouling coating the preparation method comprises the following steps:
By 59g silicone-contained acrylic resin solution latex solution, hydrogel, 1g vaseline, 1g talcum powder, the 25g cuprous oxide, 6g of 8g sustained release silicone oil
The mixture of Seanine-211 silicon vibrates 3h in a paint shaker containing porcelain bead, then with the filter mistake of 80 mesh
Filter is to get marine antifouling coating.
Embodiment 2
A kind of preparation for the hydrogel being sustained silicone oil, the specific steps of preparation are as follows:
(1) at room temperature, 18g methyl acrylate, 5g N hydroxymethyl acrylamide, 20g methyl-silicone oil, 0.1g OP-10 are added
Enter in emulsion dispersion machine, 1h is stirred with the revolving speed of 3000r/min, is then added with stirring 1.2g azo in the revolving speed of 300r/min
Two different heptonitriles, are mixed to obtain premixed material.
(2) it in four mouthfuls of reaction flasks for being equipped with blender, addition funnel, reflux condensate device, thermometer, is added
150mL water, 23g acrylamide, 5g n-isopropyl acrylamide, 0.1g OP-10, stir and evenly mix, and are warming up to 50 DEG C, then will
Premixed material is at the uniform velocity added drop-wise in acrylamide and the mixed solution of n-isopropyl acrylamide with the rate of addition of 0.5mL/min,
Solution is stirred with the rate of 1400r/min when being added dropwise, 50 DEG C is maintained and continues to be stirred to react 10h, the water of silicone oil must be sustained
Gel.
A kind of application of the hydrogel in marine antifouling coating being sustained silicone oil, marine antifouling coating the preparation method comprises the following steps:
By 54g silicone-contained acrylic resin solution latex solution, the 10g sustained release hydrogel of silicone oil, 2g vaseline, 1g lithopone, 25g cuprous oxide,
The mixture of 8g Seanine-211 silicon vibrates 4h in a paint shaker containing porcelain bead, then with the filter of 80 mesh
Filtering is to get marine antifouling coating.
Embodiment 3
A kind of preparation for the hydrogel being sustained silicone oil, the specific steps of preparation are as follows:
(1) at room temperature, by 20g methyl methacrylate, 3g N hydroxymethyl acrylamide, 2g n-isopropyl acrylamide,
20g methyl-silicone oil, 0.1g TX-10 are added in emulsion dispersion machine, with ultrasonic dispersers ultrasonic disperse 1h, then in 280r/min
Stirring at low speed under be added 1.3g benzoyl peroxide, be mixed to obtain premixed material.
(2) it in four mouthfuls of reaction flasks for being equipped with blender, addition funnel, reflux condensate device, thermometer, is added
150mL water, 25g acrylamide, 0.1g TX-10, stir and evenly mix, and 50 DEG C are warming up to, then by premixed material with 0.6mL/min's
Rate of addition is at the uniform velocity added drop-wise in the mixed solution of acrylamide and TX-10, mixed with the rate stirring of 2000r/min when being added dropwise
Solution is closed, 50 DEG C is maintained and continues to be stirred to react 10h, the hydrogel of silicone oil must be sustained.
A kind of application of the hydrogel in marine antifouling coating being sustained silicone oil, marine antifouling coating the preparation method comprises the following steps:
By 57g silicone-contained acrylic resin solution latex solution, the 8g sustained release hydrogel of silicone oil, 1g vaseline, 3g fumed silica solid particle,
25g cuprous oxide, 6g triphenylboron pyridine silicon mixture vibrate 3h in a paint shaker containing porcelain bead, then use
The filter of 80 mesh filters to get marine antifouling coating.
Embodiment 4
Embodiment 4 difference from example 1 is that: in step (1), methyl methacrylate dosage be 18g, N- methylol
Acrylamide dosage is 7g.Other are same as Example 1.
Comparative example 1
Comparative example 1 difference from example 1 is that: be not related to be sustained silicone oil hydrogel preparation, and preparation ocean
Without using the hydrogel of sustained release silicone oil during antifouling paint.Prepare the total amount and embodiment 1 of the raw material of marine antifouling coating
The total amount of the middle raw material for preparing marine antifouling coating is identical.Other are same as Example 1.
The anti-pollution of marine antifouling coating measures:
Test group is the marine antifouling coating of the embodiment of the present invention 1~3, and control group is the marine antifouling coating and sky of comparative example 1
White sample.
Anti-pollution measurement: referring to national standard " anti-fouling paint template shallow sea soak test method " (GB/T 5370-
2007), the marine antifouling coating of the embodiment of the present invention 1~3 and comparative example 1 is brushed to the poly- second in long 400mm, width 400mm respectively
On alkene material etting, test etting sample is made by wooden frame is fixed in etting；By the long 400mm of not brushing antifouling paint, width 400mm
The fixed blank etting sample that control group is made of polyethylene material etting wooden frame.Test group etting sample, control group etting sample are hung over
In the aquaculture base cage culture area of Zhejiang Ocean university of the Zhejiang Province Zhoushan island Dong Ji, after 1,3, June observation by
The result of sample, Performance Score is as shown in table 1 below.
Table 1
As can be seen from Table 1, anti-fouling effect of the marine antifouling coating of the embodiment of the present invention 1~3 in ocean is excellent, Neng Gouman
Sufficient national standard.The amount of the substance of N hydroxymethyl acrylamide in embodiment 4 is the 13% of the amount of other monomers total material, is surpassed
The framework of the present definition is crossed.Although the marine antifouling coating of embodiment 4 can meet antifouling requirement at first 3 months,
After six months, anti-pollution decline is a lot of, and it is impossible to meet the requirements of national standard.Compared with Example 1, it compares
The hydrogel of sustained release silicone oil is not added in example during preparing marine antifouling coating, though the marine antifouling coating of preparation can be
There is antifouling capacity to a certain extent, but after six months, antifouling capacity degradation, nonpolluting coating exists a large amount of impaired.It is empty
White sample performance after 1 month just has declined, and after 3 months, comprehensive performance declines the surface contamination close to after 60%, 6 month
Seriously.
Routine operation in operating procedure of the invention is well known to those skilled in the art, herein without repeating.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent structure transformation to the above embodiments, still fall within skill of the present invention
The protection scope of art scheme.
Claims (10)
1. a kind of hydrogel for being sustained silicone oil, it is characterised in that: the hydrogel of the sustained release silicone oil includes hydrogel rubber shell and bears
The methyl-silicone oil being loaded in hydrogel rubber shell, the hydrogel rubber shell are to be copolymerized by monomer A, monomer B, monomer C and monomer D
Polymer, structural formula are as follows:
Wherein, R1For H or CH3；R2For CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、CH3CH2CH2CH2One or more of；m
For the positive integer not less than 10；N is the positive integer not less than 10；P is 0 or positive integer；Q is the positive integer not less than 1, and is controlled
Corresponding monomer is no more than 10% relative to the score of the amount of other monomer total materials, and m, n, p, q value control polymer number
Average molecular weight is not less than 4000.
2. a kind of hydrogel for being sustained silicone oil as described in claim 1, it is characterised in that preparation method includes the following steps:
(1) at room temperature, surfactant, monomer A, monomer C, monomer D, methyl-silicone oil and initiator are mixed, obtains premixed material；
(2) monomer B and surfactant are added to the water, the mass volume ratio of monomer B and water is 4~5g/30mL, while stirring
45~55 DEG C are warming up to, mixed solution is obtained；Then by the premixed material in step (1) with the rate of addition of 0.5~0.75mL/min
It is at the uniform velocity added drop-wise in mixed solution, is stirred when being added dropwise with the rate of 900~3000r/min, react 9~11h, obtain sustained release silicone oil
Hydrogel.
3. a kind of hydrogel for being sustained silicone oil as claimed in claim 2, it is characterised in that: the monomer A, monomer B, monomer C
With the mass ratio of the total amount of monomer D and the total amount of surfactant, methyl-silicone oil and initiator be 240~260:1:100:6~
7。
4. a kind of hydrogel for being sustained silicone oil as claimed in claim 3, it is characterised in that: the monomer A is methyl propionate, first
Base methyl acrylate, ethyl propionate, ethyl methacrylate, propyl propionate, propyl methacrylate, isopropyl propionate, methyl
At least one of isopropyl acrylate, butyl propionate, butyl methacrylate, monomer B are acrylamide, and monomer C is that N- is different
Propylacrylamide, monomer D are N hydroxymethyl acrylamide.
5. a kind of hydrogel for being sustained silicone oil as claimed in claim 2, it is characterised in that: the surfactant is dodecane
At least one of base sodium sulphate, OP-10, TX-10, paregal O or Tween 80.
6. a kind of hydrogel for being sustained silicone oil as claimed in claim 2, it is characterised in that: the initiator be potassium peroxydisulfate,
Ammonium persulfate, V-50 initiator, azo isobutyronitrile, azobisisoheptonitrile, dioctanoyl peroxide, in benzoyl peroxide at least
It is a kind of.
7. a kind of application of hydrogel of the sustained release silicone oil as described in claim 1~6 is any in marine antifouling coating, special
Sign is: the marine antifouling coating includes silicone-contained acrylic resin solution latex solution and sustained release silicone oil hydrogel.
8. a kind of application of the hydrogel for being sustained silicone oil as claimed in claim 7 in marine antifouling coating, it is characterised in that:
The marine antifouling coating the preparation method comprises the following steps: by 25~70 parts of silicone-contained acrylic resin solution latex solution, 1~10 part of plasticizer,
5~40 parts of 1~20 part of filler material, 1~10 part of hydrogel for being sustained silicone oil and anti-fouling agent vibrate 2~4h in earthquake device together,
It is filtered with the filter of 70~90 mesh, obtains marine antifouling coating.
9. a kind of application of the hydrogel for being sustained silicone oil as claimed in claim 8 in marine antifouling coating, it is characterised in that:
The marine antifouling coating includes the raw material composition of following parts by weight: 54~70 parts of silicone-contained acrylic resin solution latex solution increases
1~4 part of agent of modeling, 1~5 part of filler material, 6~10 parts of hydrogel for being sustained silicone oil and 31~35 parts of anti-fouling agent.
10. a kind of application of the hydrogel for being sustained silicone oil as claimed in claim 9 in marine antifouling coating, feature exist
In: the concentration of the silicone-contained acrylic resin solution latex solution is 30~60wt%；Plasticizer is vaseline, chlorinated paraffin, adjacent benzene
At least one of dibutyl carboxylic acid or dioctyl phthalate；Filler material be iron oxide red, talcum powder, titanium dioxide,
At least one of lithopone, fumed silica solid particle or zinc oxide；Anti-fouling agent is cuprous oxide and/or curing four
The mixture of methyl thiuram and/or pyrithione and/or triphenylboron pyridine and/or Seanine-211.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN112175434A (en) * | 2020-08-24 | 2021-01-05 | 中国船舶重工集团公司第七二五研究所 | Anti-fouling gel particle containing rare earth/anti-fouling agent and preparation method thereof |
| CN112280389A (en) * | 2020-11-05 | 2021-01-29 | 三棵树(上海)新材料研究有限公司 | Mosquito-repellent interior wall coating added with Chinese herbal medicine extract and preparation method thereof |
| CN113214434A (en) * | 2021-04-16 | 2021-08-06 | 浙江大学 | Preparation of core-shell acrylic acid antifouling resin and application of core-shell acrylic acid antifouling resin in copper-free antifouling paint |
| CN114014971A (en) * | 2021-11-25 | 2022-02-08 | 中国海洋大学 | Preparation method and application of acrylic-based hydrogel antifouling material without volatile organic compounds |
| CN115926604B (en) * | 2021-08-20 | 2024-01-12 | 哈尔滨工程大学 | Polyurethane slow-release antifouling coating and preparation method thereof |
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| CN112175434A (en) * | 2020-08-24 | 2021-01-05 | 中国船舶重工集团公司第七二五研究所 | Anti-fouling gel particle containing rare earth/anti-fouling agent and preparation method thereof |
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| CN112280389B (en) * | 2020-11-05 | 2022-04-05 | 三棵树(上海)新材料研究有限公司 | Mosquito-repellent interior wall coating added with Chinese herbal medicine extract and preparation method thereof |
| CN113214434A (en) * | 2021-04-16 | 2021-08-06 | 浙江大学 | Preparation of core-shell acrylic acid antifouling resin and application of core-shell acrylic acid antifouling resin in copper-free antifouling paint |
| CN113214434B (en) * | 2021-04-16 | 2022-04-01 | 浙江大学 | Preparation of core-shell acrylic acid antifouling resin and application of core-shell acrylic acid antifouling resin in copper-free antifouling paint |
| CN115926604B (en) * | 2021-08-20 | 2024-01-12 | 哈尔滨工程大学 | Polyurethane slow-release antifouling coating and preparation method thereof |
| CN114014971A (en) * | 2021-11-25 | 2022-02-08 | 中国海洋大学 | Preparation method and application of acrylic-based hydrogel antifouling material without volatile organic compounds |
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